N-substituted-alkenyl-succinimides in distillate fuels



United States Patent 3,135,765 N-SUBSTETUTED-ALKENYL-SUCCRNIMIDES IN DISTILLATE FUELS Harry J. Andress, In, Pitman, and Paul 1. C. Gee, Woodbury, N.J., assignors to Socony Mobil (Bil Company, Inc., a corporation of New York No Drawing. Original application June 18, 1959, Ser. No. 821,124, now Patent No. 3,039,860, dated June 19, 1962. Divided and this application Oct. 24, 1051, Ser.

This invention relates to the improvement of nonlubrieating petroleum fractions. It is more particularly concerned with distillate fuel oils containing additives adapted to inhibit the appearance of sediments during prolonged storage periods, to prevent screen-clogging, and to prevent rusting of ferrous metal surfaces, and with gasolines adapted to prevent rusting of ferrous metal surfaces. It is well known that fuel oils are prone to form sludge or sediment during periods of prolonged storage. This sediment, of course, has an adverse effect on burner operation, because it has a tendency to clog screens and nozzles. In addition to sediment formed during storage, most fuel oils contain other impurities, such as rust, dirt, and entrained water. The sediment and impurities tend to settle out on equipment parts, such as nozzles, screens, filters, etc., thereby clogging them and causing the equipment to fail.

A further factor, incident to the storage and handling of fuel oils and gasolines, is the breathing of storage Vessels. This results in the accumulation of considerable amounts of water in the tanks, which presents a problem of rusting in the tanks. Then, when the fuel is removed for transportation, sufficient Water may be carried along to cause rusting of ferrous metal surfaces in pipelines, tankers, and the like.

It has nowbeen found that the problems of sedimentation and screen clogging in fuel oils, and of rusting with gasolines and fuel oils can be solved by the use of a single addition agent. It has been discovered that distillate fuels containing minor amounts of certain succinimides and amine salts thereof are effectively inhibited, as aforedescribed.

, Accordingly, it is a broad object of this invention to provide fuels having properties improved with novel addition agents. Another object is to provide novel succinimides. A further object is to provide a fuel oil having an additive adapted to inhibit sedimentation, to prevent screen clogging, and to prevent rusting of ferrous metal surfaces with which it comes in contact. A still further object is to provide a gasoline containing an ad- Claims.

- ditive adapted to prevent rusting of ferrous metal surfaces with which the gasoline comes in contact. A specific object is to provide certain novel succinimides and amine salts thereof and distillate fuels containing them. Other objects and advantages of this invention will become apparent to those skilled in the art from the following detailed description.

The present invention provides N-carboxymethylalkenyl-succinimides and N-(o-carboxyphenyl)-alkenyl-succinimides containing between about 8 carbon atoms and about 35 carbon atoms in the alkenyl group and the amine salts thereof with tertiaryalkyl primary amines having a tertiary carbon atom attached to the nitrogen atom and having between about 6 carbon atoms and about 30 carbon atoms per molecule; and distillate fuels containing them.

The novel addition agents of this invention are N-carboxymethyl-alkenyl-succinimides and N-(o-carboxyphenyl)-alkenyl-succinimides; and amine salts thereof with tertiaryalkyl primary amines. The succinimides contemplated herein can be prepared by several methods known .chloride with dry hydrogen chloride, and finally condens 3,135,705 Patented June 2, 1964 "ice to the art for making cyclic imides. Most feasibly, they are prepared by reacting an alkenyl succinic acid anhydride or an alkenyl succinic acid with glycine (aminoacetic acid) or with anthanilic acid, in equimolar amounts and with the elimination of water of condensation. In the case of the anhydride, there will be formed one mole of water per mole of reactant, and with the acid, two moles of water are formed. Accordingly, the condensation will be carried out at temperatures of between about C. and about 250 0, preferably between about C. and about 200 C. The time of reaction will be dependent, of course, upon the reaction temperature employed. Reaction will continue until the required amount of water of condensation has evolved. Generally, the time will vary between about 2 hours and about 6 hours. Shorter reaction times are required if Water is removed by azeotropic distillation. Suitable liquids which form azeotropes with water are non-polar solvents, such as benzene, toluene, xylenes, etc.

The alkenyl succinic acid anhydride reactant can have between 8 and 35 carbon atoms in the alkenyl radical, and preferably between 10 and 14 carbon atoms. Nonlimiting examples of the alkenyl succinic acid anhydride reactants are octenyl succinic acid anhydride, diisobutenyl succinic acid anhydride, Z-methylheptenyl succinic acid anhydride, 4-ethylhexenyl succinic acid anhydride, nonenyl succinic acid anhydride, decenyl succinic acid anhydride, undecenyl succinic acid anhydride, dodecenyl succinic acid anhydride, triisobutenyl succinic acid anhydride, tetrapropenyl succinic acid anhydride, tetradecenyl succinic acid anhydride, hexadecenyl succinic acid anhydride, ll-tricosenyl succinic anhydride, and 17- pentatriacontenyl succinic anhydride. As mentioned hereinbefore, the alkenyl succinic acids corresponding to these alkenyl succinic acid anhydrides can be used to prepare the compounds of this invention.

The amine salts of the N-carboxymethyl-alkenyl-succinimides and N-(o-carboxyphenyl)alkenyl-succinimides of this invention are prepared readily by warming the succinimide with an equimolar amount of tertiary-alkyl primary amine. The addition takes place readily, without the elimination of water, but it is facilitated by heating to temperatures of between about 50 C. and about 100 C.

The amines utilizable in forming the salts of the N- carboxymethyl-alkenyl-succinimides and N-(o-carboxyphenyl)-alkenyl succinimides are the tertiary-alkyl, primary, monoamines in which a primary amino (NH group is attached to a tertiary carbon atom and which contain between about 6 carbon atoms and about 30* carbon atoms in the tertiary-alkyl radical; and mixtures thereof. These amines all contain the terminal group,

Non-limiting examples of the amine reactants are t-hexyl primary amine, t-octyl primary amine, t-nonyl primary amine, t-decyl primary amine, t-dodecyl primary amine, t-tetradecyl primary amine, t-octadecyl primary amine, teicosyl primary amine, t-docosyl primary amine, t-tetracosyl primary amine, and t-triacontyl primary amine. The amine reactants can be prepared in several ways well known to those skilled in the art. Specific methods of of preparing the t-alkyl primary amines are disclosed in the Journal of Organic Chemistry, vol. 20, page 295 et seq. (1955). Mixtures of such amines can be made from a polyolefin fraction (e.g., polypropylene and-polybutylene cuts) by first hydrating with sulfuric acid and water to the corresponding alcohol, converting the alcohol to alkyl tillate fuel oils, or mixtures of straight-run ing the chloride with ammonia, under pressure, to produce a t-alkyl primary amine mixture.

The N-carboxymethyl-alkenyl-succinimides and N-(ocarboxyphenyl)-alkenyl-succinimides of this invention andthe aminesalts have the structures, respectively:

. tain all three The amount N-carboxymethyl-alkenyhsuccinimide, N-(o-carboxylphenyl):alkenyl-succinimide or amine salt to distillate fuel in accordance with 200 pounds per thousand barrels of oil (about 0.08 Weight wherein R is an alkenyl group containing between 8 35 carbon atoms, atoms, and R is a .tertiary-alkyl radical tween about 6 and about carbon atoms. 1 The fuel oils that are improved in accordance with this invention are hydrocarbon fractions having an initial boiling point of at least about.100 point no higher than about 750 F., and boiling substantially continuously throughout their distillation range. Such fuel'oils are generallyknown as distillate fuel oils. It is to be understood, however, that this term is-not restricted to straight-run distillate fractions. The distillate fuel oils can be straight-run distillate fuel oils, catalytically or'thermally cracked (including hydrocracked) disdistillate fuel oils, naphthas and the like, with cracked distillatestocks. Moreover, such fuel oils can be treated in accordancewith well known commercial methods, such .as, acid. or caustic treatment, hydrogenation, solvent refining, -clay treatment,etc. f Q1.

The distillate fuel oils are characterized by. their relatively low viscosities,

containing behydrocarbons, however, is the distillation range. As mentioned hereinbefore, this range-will lie between-about 100 F. and about 750 range of each individual boiling'range falling, nevertheless, Withinthe above-specified limits. Likewise, each fueloil will boil substantial! ly continuously throughout its distillation range.

Particularly, contemplated among the fuel oils are Nos. 1, Zjand 3, fuel oils used in oils, and the jet combustion fuels. The domestic fuel 'oils generally conform to thespecification's set forth in ASTM Specification D396-'48T. Specifications for diesel fuels,

F.. and an end-boiling heating and as diesel fuel 7 preferably between 10 and 14 carbon percent) will be employed. It may not always be desired, however, to accomplish an three aforementioned results. In such cases, where it is desired to elfectxonly one or two results, lower concentrations can be used. Thus,

if it is desired only to prevent rust under dynamic con:

ditions, as in a pipeline, it has been found that concentrations as low as about 5 p.p.m., i.e., about one pound of additive per thousand barrels. of oil (about 0.0004. 7 weight percent), are effective.

In gasoline the concentration of additive will varybetween about 0.0004 percent an d about 0.5 i p preferred practice, amounts. varying between about 0.005 percent and aboutOrOS-percht, by weight, are used. In

, general, therefore, the amount of succinimide of this invention or of amine salt thereof that can be added to pour points, and the like. The' 'i' '11 t' t t ItJC. Principal Property 111;: cnarac erizes be con emp '4 ed 011s, f i r p r u o ia d d Comment tillate oils having viscositi'es within the range of from, ;about to about'500..S.U.S.-at 100 F.. Synthetic oils,

F. Obviously, the distillation 7 fuel oil Will cover a narrowerv are defined in ASTM Specifications D975-48Tn Typical jet fuels are defined in Military Specification;'MlL'F-- 56243.

The motorfuels contemplated herein are inixturesof hydrocarbons suitable for use in internal combustion en? gines of the spark-ignition type. These fuels include both motor gasolines and aviation gasolines. gasolines have an initial boiling'po'int as low as about 80 F. and an end-boiling point as'high as about 440 F. and

' boils substantially continuouslyfbetween the initialboil ing point and the end-boiling on the other hand, are mixtures of hydrocarbons having an initial boiling point of'about'80 point of about'340 F. and

boiling substantially continuously between these points. 7 a w u point. Aviation gasolines,"

In general, motor 1 1 of a tertiary'butyl dodecyl' amine,

amine, and r'elatively small amounts, i.e., less'thanaboutf. ,5 percent of "amineshaving' less than 121orn'1orethanl5 F. and'an'e'ndQboiling thereof and fuels, as

' as those skilled in the 'artwill readily'appreciate J v v g MtoAcIbsANn sALTsz i yThe salt-forming amine reac'tant used infthe 'spec ific working examples the distillate fuel, 'inorder to achieve a beneficial result,

will vary generally between about one pound per thousand barrelsof fuel and about 200 pounds'per thousand'barrels of fuel. Preferably, it will vary between about 10 pounds and about 200 pounds per thousand barrels. of fuel.

If it'is desired, 7

other additives-for Thus, for example, there can be present foam inhibitors: and ignition and burning quality 'impi overs. of 'suchadditives" are silicones, dinitropropane, amyl .ni-. trate, metal sulfonates, and thellike. 7

I The additives of the invention may bepused. in the gasoline along with other additives designed. to impartother improved properties thereto.

agentsQanti-stall, additives, pre-i gnition inhibitors,imetal-' deactivators, dyes, antioxidants, detergents, etc.', maybe present in the gasoline. a small amount,.from about ,0.01 percentto'albout'l per cent, by weight, of a solvent oil or upperlube, ,Suitable may also be used.

illustrating the to be, strictly understood, however, that tives and fuels, described therein.

Other succinimides or amine salts discussed hereinbefore,can be used,

is a mixture ofpure minesl A is amixture of primary amines having a carbon atom In mostcase's, in Whichit'is desired to ob-- percent, by weight, of the gasoline; In

the fuel oil compositions can contain the purpose of achieving other results. v

Examples 7 Thus, anti-knock .Also, the gasoline may contain 7 or to the operations andjm'anipulations.

" The following specific examples arefor the purpose of additives and the fuel compositions {of this: invention; and" of exemplifying the: specific nature. thereof. It 'is i this invention is notto be'llimited by the, particular addi "fA'mine w 0 group attached to t-he"amino (+N I-I );J V

groupandcontaining 12 to l;5- carbon -atom s p err'aminei l f c i and averaging lZ .carbon atomsiperf molecule." Q

This mixture contains,.by'weighnabout'85 percent' tertiary about '10, percentgtertiary pentadecylf 5 carbon atoms".

Example 1 A mixture of 37.5 grams (0.5 mol) glycine and 150 grams (0.5 mol) tetrapropenyl succinic anhydride were slowly heated to a temperature of about 200 C. over a period of about 12 hours. Nine grams (0.5 mol) of water were evolved during the course of the reaction.

Example 2 Example 3 A mixture of 75 grams (0.55 mol) anthranilic acid and 150 grams (0.55 mol) tetrapropenyl succinic anhydride were slowly heated to a temperature of about 200 C. over a period of about 12 hours. Ten grams (0.55 mol) of water were evolved during the course of the reaction.

SEDIMENTATION The test used to determine the sedimentation characteristics of the fuel oils is the 110 F. Storage Test. In this test, a SOD-milliliter sample of the fuel oil under test is placed in a convected oven maintained at 110 F. for a period of 12 'weeks. Then, the sample is removed from the oven and cooled. The cooled sample is filtered through a tared asbestos filter (Gooch crucible) to remove insoluble matter. The weight of such matter in milligrams is reported as the amount .of sediment. A sample of the blank, uninhibited oil is run along with a fuel oil blend under'test. The effectiveness of a fuel oil containing an inhibitor is determined by comparing the weight of sediment formed in the inhibited oil with that formed in the uninhibited oil.

Additives described in the examples were blended in test fuel oil and the blends were subjected to the 110 F. Storage Test. The test results comparing the blended fuels and uninhibited fuels are set forth in Table I. The test fuel oil was a blend of 80 percent distillate stock obtained from continuous catalytic cracking and 20 percent straight-run distillate stock. It has a boiling range of between about 320 F. and about 640 F. and is a typical No. 2 fuel oil.

TABLE I.110 F. STORAGE TEST12 WEEKS Cone'n, lbs./1,000 bbls.

Sediment,

Additive of Example rug/liter SCREEN CLOGGING The anti-screen clogging characteristics of a fuel oil were determined as follows: The test is conducting using a Sundstrand V3 or S1 home fuel oil burner pump with a self-contained 100-mesh Monel metal screen. About 0.05 percent, by weight, of naturally-formed fuel oil sediment, composed of fuel oil, water, dirt, rust, and organic sludge is mixed with liters of the fuel oil. This mixture is circulated by the pump through the screen for 6 hours. Then, the sludge deposit on the screen is washed off with normal pentane and filtered through a tared Gooch crucible. After drying, the material in the Gooch crucible is washed With a 5050 (volume) acetone-methanol mixture. The total organic sediment is obtained by evaporating the 'pentane and the acetonemethanol filtrates.

, Drying and weighing the Gooch crucible yields the amount of inorganic sediment. The sum of the organic and inorganic deposits on the screen can be reported in milligrams recovered or converted into percent screen clogging.

Blends were prepared in the aforedescribed test fuel oil and subjected to the Screen Clogging Test. Results are set forth in Table II.

TABLE II.SCREEN CLOGGING The method used for testing anti-rust properties of gasolines was the ASTM Rust Test D-665 operated for 48 hours at F. using distilled water. This is a dynamic test that indicates the ability to prevent rusting of ferrou metal surfaces in pipelines, tubes, etc.

Blends of the additives described in the examples in the test gasoline were subjected to the ASTM Rust Test D-665. This test gasoline was a blend of 80 volume percent catalytically cracked gasoline and 20 volume percent straight-run gasoline, which had a boiling range of F. to 400 F. Pertinent data are set forth in Table III.

TABLE IIL-ASTM RUST TEST D-665 The Static Rust Test similates conditions encountered in storage tanks, such as, the home fuel oil storage tank. In this test, a strip of 16-20 gauge sand blasted steel plate is placed in a clear quart bottle. The length of the strip is suflicient to reach from the bottom of the bottle into the neck of the bottle without interfering with the cap. One hundred cc. of synthetic sea water with pH adjusted to 5 (ASTM D-665) and 750 cc. of test oil are placed in the bottle. The bottle is capped tightly, shaken vigorously for one minute, and permitted to stand quietly at 80 F. for 21 days. At the end of that time, the amount of rust that occurs on the surface of the plate immersed in the water is used as a measure of elfectiveness of the fuel to inhibit rusting in storage vessels. It is generally preferred that no more than 5 percent of the surface should be rusted. This test is much more severe than the ASTM Rust Test. Many additive compositions that pass the ASTM test fail in the Static Test. On the other hand, materials that pass the Static Test always pass the ASTM test.

Blends of additives in the aforedescribed test fuel oil were subjected to the Static Rust Test. Pertinent results are set forth in Table IV.

TABLE IV.STATIC RUST TEST Oonen, Percent Additive of Example lbs/1,000 Rusting bbls.

'Rl'mlr 100 1 25 O 2 25 0 7 improvement, many of the additives can be used in relatively small amounts, as for dynamic rust prevention. If, on the other hand, it is desired to accomplish all the aforementioned beneficial results, this can be accomplished at the practical additive concentration of 50-100 pounds per thousand barrels of fuel oil.

The present application is a division of copending application, Serial No. 821,124, filed June 18, 1959, now

Patent No. 3,039,860.

Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as t those skilled in the art will readily understand; Such variations and modifications are considered to be within the purview and scope of the appended claims.

What is claimed is: r I

1. N-carboxymethyl-tetrapropenyl-succinimide.

2. An amine salt of N-carboxymethyl-tetrapropenyl s'uccinimide, wherein the salt-forming amine is a mixture of tertiary-alkyl primary amineshaving a tertiary carbon atom attached to the amino group and having between 12 and 15 carbon atoms per amine molecule and averaging about 12 carbon atoms per molecule.

3. N-(o-carboxyphenyl) -tetrapropeny1 succinimide. 4. A composition of matter selected from the group consisting of: (1) an N-carboxymethyl-alkenyl-succinimide having the structure t orn-o r t t (.2) an N-(o-carboxyphen l)-alke'nyl-succinimide having the structure I s v to. 1

. COOH RCH (3) an amine salt of (1) having the structure fl' RCHC\ it NOH;COOHNH,R'

(4) and anamine salt of (2) having the structure"; 1 i

V ooonnn n' R-OH-C 7 1 wherein Ris an alkenyl group having between about 8 7 and about'35 carbon atoms, and R is atertiary-alkylf radical containingbetween about 6 and aboutj3'0 carbon atoms, the tertiary carbon atom of which is attached to the nitrogen atom. M

' No references cited.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,135,765 June 2, 1964 Harry J. Andress Jro et al a It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 65, strike out "of"; column 3, lines 6 to 12, the right-hand structure should appear as shown below instead of as in the patent:

fi RCH C NCH2COOHNH2R CH -fi column 5, line 61, for "conducting" read conducted Signed and sealed this 6th day of October 1964.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,135,765 June 2, 1964 Harry J. Andress, Jro et ale It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 65, strike out "of"; column 3, lines 6 to 12, the right-hand structure should appear as shown below instead of as in the patent:

O R-CH C! N-CHZCOOHNHZR cH- c A column 5, line 61, for "conducting" read conducted Signed and sealed this 6th day of October 1964.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

4. A COMPOSITION OF MATTER SELECTED FROM THE GROUP CONSISTING OF: (1) AN N-CARBOXYMETHYL-ALKENYL-SUCCINIMIDE HAVING THE STRUCTURE 